Polymerization of unsaturated compounds having the cyclopentadiene nucleus



Patented Mai-. 30, 1943 POLYMERIZATION OF UNSATURATED COM- POUNDS HAVING THE CYCLOPENTADIENE NUCLEUS 1 a Frank J. Soday, Upper Darby, Pa.,-assizno'r to The United Gas Improvement Company, a corpora.-

tion of Pennsylvania No Drawing. Application April 2 5, 1938,

Serial No. 204,229.

Ill Claims.

This invention pertains generally to the catalytic polymerization of unsaturated compounds such as cyclopentadiene and pertains particularly to the use of zinc chloride-organic solvent complexes as catalysts.

The invention will be described in connection with the production of cyclopentadiene polymer of a specific type; However, it is to be understood that it may be employed in the production of polymers of other types.

Cyclopentadiene may be polymerized into at least two broad types of polymers one of which is characterized by being soluble in solvents such as benzene, toluene, chloroform, carbon tetrachloride and high flash naphtha, while the other is characterized by. being insoluble in'these solvents.

The polymerization is usually carried out while the cyclopentadiene is in solution in a solvent.

I have discovered that the soluble type of polymer may be produced with zinc chlorideorganic solvent complexes, and particularly zinc chloride-ether complexes, by a careful control of the polymerizing reaction.

Examples of zinc chloride complexes are ,zinc chloride-dimethyl ether complex, zinc chloridediethyl .ether complex, zinc chloride-di-isopropyl ether complex, zinc chloride-di-isobutyl ether complex, zinc chloride-dl-N-butyl ether complex, zinc chloride-methyl isopropyl ether complex, zinc chloride-ethyl isopropyl ether complex, zinc chloride-methyl phenyl ether complex, and zinc chloride-ethyl phenyl ether complex. I

The preparation of complexes of this character in general comprises adding zinc chloride to the solvent with agitation. As a result, if a reaction takes place, a definite chemical compound is formed.

There are at least four factors which influence production of soluble polymer. These four factors are. (1) temperature, (2 concentration of cyclopentadiene, (3) proportion of uniformly distributed catalyst and (4) time.

Generally speaking, and all other conditions remaining the same, it appears that there is a threshold temperature for the formation of insoluble polymer, and that at all temperatures below this threshold temperature the soluble polymer results. It is recognized, that high concentrations of cyclopentadiene and/or high proportions of uniformly distributed catalyst might place this theoretical threshold temperature below commercially obtainable temperature levels. However, for reasonable concentrations of cyclopentadiene and reasonable proportions of uniformly distributed catalyst at threshold temperature can be shown to exist for any given concentration of cyclopentadienewith any given proportion of uniformly distributed catalyst.

Also generally speaking, and all other conditions remaining the same, it appears that there is a threshold concentration of cyclopentadiene forfthe formation of insoluble polymer, and that at all concentrations below this threshold concentration the soluble form of-polymer results. The term concentration of cyclopentadleneas used herein and in the claims specifies the percentage by weight of total cyciopentadiene.

whether reacted or not, after all of the materials have been combined. It is recognized that inordinately high temperatures and/or inordinately high proportions of uniformly distributed cataany. given proportion of uniformly distributed catalyst.

Also generally speaking, and another conditions remaining the same, and assuming that all of the materials'have been combined. it appears that there is a threshold proportion of uniformly distributed catalyst for the formation of insoluble olymer, and that with all proportions below this threshold the soluble polymer results. In this connection experiments indicate quite clearly It is recognized that inordinately high temperatures and/or inordinately high concentrations of cyclopentadiene may make the theoretical threshold proportion of uniformly distributed catalyst difiicult of determination. However, for reasonable temperatures and reasonable, concentrations of cyclopentadiene a threshold proportion of uniformly distributed catalyst can be x are examples.

shown to exist at any given temperature with any given concentration of cyclopentadiene.

Also generally speaking, and all other conditions remaining the same, it appears that there is a threshold reaction time for the formation of insoluble polymer, and that for all reaction times below this threshold reaction time the" soluble polymer results. It is recognized that low temperatures, low concentrations of cyclopentadiene, and/or low proportions of uniformly distributed catalyst may cause this theoretical threshold reaction time to approach infinity.

On the other hand high temperatures, high concentrations of cyclopentadiene and/or high proportions of uniformly distributed catalyst may cause this theoretical threshold reaction time to approach zero. However, for reasonable temperatures, for reasonable concentrations of cyclopentadiene, and/or for reasonable proportions of uniformly distributed catalyst, a threshold reaction time can be shown to exist.

. Threshold reaction time, however, differs from v the other three factors in that when the threshold reaction time becomesmore than one hour the time necessary to-form insoluble polymer ap- Fiu'thermore, the exactvalues of (1) temperature, (2) concentration of cyclopentadiene, (3) proportion of uniformly distributed catalyst and (4) time at which insoluble polymer; begins to catalyst or solvent. However, .the exact values may be readily determined by test.

-' appear may vary somewhat with change in The soluble polymer obtained varies in physical characteristics with the solvent used during the polymerization. For instance soluble polycyclo Lpentadienes obtained by polymerizing cyclopentadiene by my new process in solvent =-naphtha, toluene, or benzene differ somewhatv from each other as shown,- for example, in the.v

suitability of these polycyclopentadienes for coating metals for whichthey are unusually well 5 suited. As an illustration, forcertain purposes the benzene polymer is superior, the, toluene polymer coming next but being, nevertheless, par-v ticularly well suited.

Accordinglyyin the preparation of my poly-z merized cyclopentadiene a solution of cyclo-- 1 crease in temperature. These polymers are compentadiene in a chosen solvent such as toluene is employed.

x I use as catalyst one or more zinc chlorideorganic solvent complex and particularly one.or

more zinc chloride ether complex. Zinc chloride itself is generally unsatisfactory.-

The complex catalysts may be employed as such, or in the form of suspensions, emulsions,

or solutions in organic solvents of which benzene,

toluene, solvent naphtha and petroleum naphtha Such suspensions, emulsions, or

solutions are formed by adding the catalyst to the solvent followed by stirring. As an example, I find that a concentration of zinc chloride com- .plex in toluene of 10.0% by weight of toluene is suitable as a catalyst suspension although any other concentration or solvent suitable for the purpose may be employed. 4

The reactants should not be combined too rapidly since under such circumstances the reaction may proceed too violently and cause local overheating with the production of insoluble polymer, or undesirable color bodies, or both, which it is proposed to avoid.

The catalyst may be added to the solution of cyclopentadiene, particularly when the catalyst itself is in solution or in suspension in a solvent, or the solution of cyclopentadiene may be added to. a suspension, emulsion or solution of the catalyst. The reaction proceeds much more smoothly than when the catalyst is added to the cyclopentadiene. In the latter case no reaction appears to take place until a certain catalyst concentration is'reached.

In either event, however, the addition of one material to the other is preferably accompanied by thorough stirring which is preferably rapid to insure uniform distribution not only of the materials but also of temperature.

In addition the reaction is preferably carried out in apparatus capable of temperature-control such as a jacketed vessel provided with an agitator.

Avery effective control of the temperature of I the reaction and of local superheating is afforded when the preferred procedure is followed.

, As an example, the proportion of catalyst may conveniently be between 0.5% to 25.0% by-weight of cyclopentadiene provided the temperature ofthe reaction is controlled and/or the concentration of cyclopentadiene is sufilciently low, thus avoiding the formation of insoluble'polymer.

A'proportion of catalyst of 10.0% by weight of the total cyclopentadiene present is found to be convenient. It permits variation in temperatures and in concentrations of cyclopentadiene without the formation of insoluble polymer.

maining the same, higher proportions of catalyst yieldpolymers of higher molecular weight. This islavery pronounced when the reaction temperature is. 0 C., but is much'lessp'ronounced at or instance, j... at all temperatures below 50 Citgel-like polymers are obtained when high proportions of catalyst are employed just below mer as shown above.

indicate definitely the threshold conditions. Thelease with which gellike polymers are obtained increases 'with delncidentally; th 'fformation of gel does not Discoloration of theproduct appears to increase and decrease with increase and decrease in proportion of catalyst so that lower proportions of catalyst yield materials of lesser discoloration.

Temperatures above, 100 C. are preferably avoided and it is recommended that great care be taken to keep the temperatures throughout presence of insoluble poly- On the other hand, at C. and even though the proportion of catalyst is fairly high, surprisingly light colored polymers are obtained.

Low reaction temperatures are therefore indicated.

Cyclopentadiene solutions of any suitable concentration can be used, keeping in mind what has been said with respect to threshold condi tions, although I more often employ concentrations of cyclopentadiene 'of from 20 to 30% by weight of total reactants.

Incidentally it appears that 1 the molecular weight of the resulting soluble polycyclopenta- -diene may be varied somewhat by varyingthe concentration of cyclopentadiene in the starting material. Other conditions remainin the same, higher'concentrations of cyclopentadiene yield materials of higher molecular weight.

In summing up it may be said that higher molecular weight polymer can be made more advantageously at .lower temperatures, with higher cyclopentadiene concentrations, and with high proportions of catalyst. Under the recommended conditions the polymer is formed in good yield and with a satisfactory color.

The chosen time for the reaction may vary considerably keeping in mind what has been said about threshold conditions. I find that for practicable purposes and goodyields other conditions should be chosen such that the reaction. time is. somewhere in theneighborhood of one hour or more. This is borne out by the fact that the yield increases with reaction time up to a merized material represented by the lower layer certain point. The time is, of course, preferably chosen to obtain good yields.

The following specific example will serve to further illustrate the'invention.

21 grams of zinc chloride-diethyl ether complex (containing 11 grams ZnClz) was added to a mixture of 70 grams of cyclopentadiene and 70 grams of benzene during a, period of 10 minutes at a temperature 'of 0 to 5 C. The mixture was stirred for 2 hours at 20 0., and then permitted to settle whereupon two layers wereformed. The layers were separated and the clear supernatant layer was hydrolyzed with 50 grams of 20% sodium carbonate solution. After agitating for 1 hour, 50 grams of CaO was added and the agitation continued for an additional period of one hour. A small quantity of filter cel was added and. the mixture filtered.

The lower layerof polymerized material was washed with benzene and alcohol was added to precipitate the resin. The precipitated material was redissolved in benzene, neutralized with a NazCOa solution and filtered.

The combined filtrates contained 17.6 grams of polycyclopentadiene of excellent quality.

No insoluble polymer was obtained. In the above example more or all of the polymight have been held insolution by adding more benzene at the beginning or during vthe course of the reaction.

"Furthermore, instead of separating and sep arately treating the layers, suflicient benzene might have been added after the reaction was complete to take into solution in the upper layer all of the polymerized material of the lower layer, that is, suflicient benzene to cause the layers to disappear into a single solution. Such solution would then be treated the same as the upper laye as set forth above.

: The zinc chloride-diethyl ether complex used in the foregoing example was made by adding ll gramsof freshlymade anhydrous zinc chloride to 10 grams :of .diethyl ether. The mixture was agitated in a closed flask duringwhichheat was evolved. All of the zinc chloride dissolved.

The solution was filteredand the catalyst was then ready for use.

Generally speaking, any other zinc chlorideorganic solvent complex might be 1' substituted. This'applies particularly to the'zincv chlorideether complexes.

In the above specific example the cyclopentadiene is in diluted form before addition.

The addition of water or a water solution as.

above to hydrolyze the catalyst makes it possible not only to completelyremove the activity of the catalyst and thus stop the reaction. at any point, but also makes it possible to remove the. corrosive and discoloring acid constituents of the catalyst by a'suitable. alkali. The alkali is preferably added with the water used to hydrolyze the catalyst, although it may be added later if desired. The failure. to substantially completely remove the catalyst and its hydrolysis products may be the cause of serious discoloration. The

insoluble reaction products formed during the hydrolysis and neutralization remain behind on the filter leaving a highly purified filtrate.

Thisnpolymer may be used as such, or it may be 'concentrated in a vacuum still of suitable design to give'a product containing any desired higher concentration of polycyclopentadiene, including solid polycyclopentadiene, or it might be diluted to give any desired lower concentration.

' or a second solvent might be substituted such as.

a higher boiling solvent. This may be. done either before or after concentration by adding the second solvent and distilling.

In the above example the particular temperatures were chosen to control the physical prop erties such as viscosity and color of the product.

It will be noted that at no time did the temperature exceed C. or even 70 C. .The manner of combining 'the reactants, constant agitation, and brine cooling made it possible to prevent local overheating, and the formation of insoluble polymer. t

In the above examples (1) temperature, (2) concentration of cyclopentadiene, (3) proportion of uniformly distributed catalyst, and (4) reaction time may be varied considerably in the production of soluble polymer having in mind what has been said withrespect to threshold conditions. If it is found that insoluble polymer is obtained, one or more of the four conditions, namely (1) temperature, (2) concentration of cyclopentadiene, (3) proportion of catalyst, and (4) reaction time should be reduced until the soluble polymer isobtained. 1

Carrying out the polymerization in the presshould not exceed 70 C.,.concent'rations of cyclopentadiene should rarely exceed 50%. by weight of the total solution except possibly at low temperatures, and concentrations of uniformly distributed catalyst should rarely exceed 25% by weight of cyclopentadiene.

It should-be kept in mind that there are for practical purposes minimum values for tempera- -.ture, concentration of cyclopentadiene, proportion of catalyst and time, which practice will show ought to be exceeded to obtain reasonable yields. n the other hand, if the maximum values given in the previous paragraph for temperature, catalyst and cyclopentadiene were used simultaneously, insoluble polymer might be formed, even though the reaction time chosen were as short as good practice would permit.-

It is by the observanceofthepreferred principles set forth herein that a quality product is produced in good yield.

While in the above specific examples toluene is used -as a polymerization medium, it is to be understood that other suitable solvents may be substituted of which benzene, xylene, ethyl ben- ;'zene,.solvent naphtha, petroleum naphtha, carbon tetrachloride, and ethylene dichloride are examples. The products with benzene and toluene are preferred for specific uses'as hereinafter referred to.

Although in the above particular description the cyclopentadiene isdiluted before the addinon of the catalyst, it is. to be understood that variations are possible, For instance it. is con- "ceivable that all of the diluent may be first mixed with one of the reactants (either catalyst or unsaturated compound) and that the other reactant may be added in concentrated form, particularly, if the principles set forth herein are closely observed. diluent may be added to one of the reactants so that the other" is relatively concentrated. It is also conceivable that, with the exercise of extreme care and the closest adherence to the principles set forth herein, both reactants might pos- Or the larger part of the V of insoluble material present, such as the neutralizing agent, is then effected by filtering the partially concentrated solution after the complete removal of the water presentby distillation. After this step the solution can be further concentrated if desired.

The product may be used for many purposes, for instance, for lacquers generally, for varnishes either alone or in admixture with other resins, for enamels, for paints, or in fact for coating compositions generally. It is ideally suited to the coating of metals, for instance, for the coating of food containers as described and claimed in eopending application, Serial Number 291,007, filed August 19, 1939, by Newcomb K. Chaney. This is especially true of the products polymerized in benzene and toluene.

If desired, it is possible to obtain soluble polycyclopentadiene of higher viscosity or of otherwise changed characteristics by starting with a solution of polycyclopentadiene and stopping the reaction before threshold conditions are exceeded. 7

While the invention has been particularly described in connection with the polymerization of cyclopentadiene, it is to be understood that it is applicable to the polymerization of substituted cyclopentadienes having the cyclopentadiene nucleus containing the characteristic conjugated double bonds. However, it is to be understood that the polymer particularly described has certain uniquecharacteristics which distinguish it from polymers prepared from other starting materials. Examples of such other sibly be employed in relatively concentrated form. Other variations are possible. Whenadding one liquid to another with agitation I find it convenient and often preferable to do this below the surface of one of the liquids.

Any-other suitable alkali such as sodium hydroxide, sodium carbonate, sodium bicarbonate, magnesium hydroxide, an aminev or other basic substance might, be substituted for quicklimein the above specific examples, followed by a nonacidic drying agent such as Na2SO4, or soda lime. Both neutralization and drying is effected by 09.0.

In case itis desired to form a highly concentrated solution of polycyclopentadiene, or to isolate it'in solid form, it is not necessary to dry the solution after neutralization as the water present can be readily removed in the subsequent concentrating operation. The complete removal compounds are the alkyl, aryl, and alkyl-aryl.

It is to be understood that the above specific examples are byway of illustration. Therefore, changes, omissions, additions, substitutions, and/or modifications might be made within the scope of the claims without departing from the spirit of the invention which is intended to be limited only as required by the prior art.

I claim;

l. A process for producing benzene-soluble cyclic diene polymer by the catalytic polymerization of a cyclic diene compound selected from the class -.of cyclic dienes consisting of cyclopentadiene, alkyl. substituted cyclopentadiene and aryl substituted cyclopentadiene in the sub stantial absence of polymerizable compounds not contained-in said class, comprising mixing with said cyclic diene in the presence of a solvent to effect said polymerization in considerable proportion to said cyclic diene polymer a hydrolyzable zinc chloride-organic solvent complex previously formed byreacting zinc chloride with an organicsolvent capable of reacting with zinc chloride to form said hydrolyzable complex; and preventing the polymerization of said cyclic diene from being effected entirely to benzene-insoluble cyclic diene polymer by thoroughly agitating the reaction mass while maintaining the reaction 50% by weight, and the sence of polymerizable compounds not contained in said class, comprising mixing'with said cyclic diene in the presence of a solvent to eflect saidacting zinc chloride-with an organic solvent ca pable of reacting with zinc chloride to form said hydrolyzable complex; and preventing the polymerization of said cyclic'diene from being efiected largely to benzene-insoluble cyclic diene polymer by thoroughly-agitating the reaction masslwhile maintainingthe reaction temperature below, 70 C., the concentration of said cyclic diene below proportion of catalyst, to said cyclic diene below %by weight, andby stopping the reaction by inactivating said catalyst while benzene-soluble cy'clicdiene polymer isthe preponderant polymer present in the reaction mass.

3. A process for producing benzene-soluble polycyclopentadiene by the catalytic polymerization of cyclopentadiene in the substantial absence of polymerizable compounds other than cyclic dienes selected from the class of cyclic dienes consistingof cyclopentadiene, alkyl substituted cyclopentadiene a'ndaryl substituted cyclopentadiene, comprising mixing with said cyclopentadiene in the'presence of'a solvent to effect said polymerization'in considerable" proportion" to polycyclo pntadiene a hydrolyzable zinc chloride-organic solvent complex previously-formed by reacting zinc chloride with an organic solvent capable of reacting with zinc chloride to form said hydrolyzable complex; and preventing the polymerization of said cyclopentadieneirom being efiected entirely to benzene-insoluble polycyclopentadiene by thoroughly agitating the reaction mass while maintaining the reaction temperature below 70 0., the concentration of said cyclopentadiene below 50% by weight, and the proportion of catalyst to said cyclopentadiene below by weight, and by stopping the reaction by inactivating said catalyst while benzene-soluble polycyclopentadiene is present in the reaction mass.

4. A process for producing benzene-soluble polycyclopentadieneby the catalytic polymerization of cyclopentadiene in the substantial absence of polymerizable compounds other than cyclic dienes selected from the class of cyclic dienes consisting of cyclopentadiene, alkyl substituted cyclopentadiene and aryl substituted cyclopentadiene, comprising mixing with said cyclopentadiene in the presence of a solvent to efiect said polymerization in considerable proportion to polycyclopentadiene a hydrolyzable zinc chloride organic solvent complex previously formed by reacting zinc chloride with an organic solvent capable of reacting with zinc chloride to form said hydrolyzable complex; and preventing the polymerization of said cyclopentadiene from being effected largely to benzene-insoluble polycyclopentadiene by thoroughly agitating the reaction mass while maintaining the reaction temperature below 70? C., the concentration of said cyclopentadiene be low 50% by weight, and the proportion of catalyst to said cyclopentadiene below 10% by weight, and by stopping the reaction by inactivating said catalyst while benzene-soluble polycyc1opentadiene is the preponderant polymer present in the reaction mass.

5. A process for producing benzene-soluble polycyclopentadiene by the catalytic polymerization of cyclopentadiene in the substantial absence of polymerizable compounds other than cyclic dienes selected from the class of cyclic dienes con-.

sisting of cyclopentadiene, alkyl substituted cyclopentadiene, and arylsubstituted cyclopentadiene,

pentadiene a hydrolyzable zinc chloride-organic solvent complex previously'formed by reacting zinc chloride with an organic solvent capable of reacting with zinc chloride to form said hydro: lyzable complex; and substantially completely preventing the conversion of said cyclopentadiene to benzene-insoluble polycyclopentadiene by thoroughly agitating the reaction mass while maintaining the reaction temperature below C., .the concentration of said cyclopentadiene below 50% by, weight, and the said cyclopentadiene below 10% by weight, and by stopping the reaction by inactivating said ,catalyst beforesubstantially any benzene-insoluble polycyclopentadiene is present in the reaction mass.

6. A process for producing benzene-soluble polycyclopentadiene by the catalytic polymerizationtof cyclopentadiene in the substantial absence of polymerizable material other than cyclic dienes selected from the class of cyclic dienes consisting of cyclopentadiene,=alkyl substituted cyclopentadiene and aryl substituted cyclopentadiene, comprising diluting said cyclopentadiene with a suitable solvent, diluting with a-suitable solvent a hydrolyzable zinc chloride-organic solvent complex previously formed byreacting zinc chloride with/an organic solvent capable of reacting'with zinc chlotide to form said hydrolyzable complex, jeflecting :said polymerization in considerable proportion to polycyclopentadiene by slowly adding saldsolution of cyclopentadiene to said diluted catalyst with thorough mixing while maintaining the reaction temperature below 70 C., the con centration of said cyclopentadiene below 50% by weight, and the proportion of catalyst to said cyclopentadiene below 10% by weight, and stopping the reaction by inactivating said catalyst before substantially any benzene-insoluble polycyclopentadiene is present in the reaction mass.

7. A process for producing benzene-soluble polcyclopentadiene by thoroughly agitating the reac-' tion mass While maintaining the reaction tem perature below 70 C.,' th concentration of said cyclopentadiene below 50 proportion of catalyst to said cyclopentadiene below 25% by inactivating said catalyst while benzene-soluble polycyclopentadiene is the preponderant polymer present in the reaction mass.

- 8. A process for producing benzene-soluble polycyclopentadiene by the catalytic polymerization of cyclopentadiene in the substantial absence of all other compounds polymerizable under the proportion of catalyst to by reacting zinc chloride with anby weight, and-the I by weight, and by stopping the reaction form said hydrolyzable complex;

the polymerization 9. A process for producing benzene-soluble polycyclopentadiene by the catalytic polymerization of cyclopentadiene in all other compounds polymerizable under the conconditions obtaining, comprising mixing with said I in the presence of a solvent to tion mass'while maintaining the reaction temperature below 45 0., the concentration of said cyclopentadiene below 50% by weight, and the proportion of catalystto said cyclopentadiene below 10% by weight, and by stopping the reactionby inactivating said catalyst while benzene-soluble V polvcyclopentadiene is the preponderant polymer catalyst while benzene-solubie polycyclopentadiene is present in the reaction the substantial absence of ditions obtaining, comprisingmixing with said cyclopentadiene in the presence of a solvent to eflect said polymerization in considerable proportion to polycyclopentadiene a hydrolyzable zinc chloride-organic solvent complex previously formed by reacting zinc chloride with an organic solvent capable or reacting with zinc chloride to iorm said hydrolyzable complex; and preventing the polymerization of said cyclopentadiene from being efiected largely to benzene-insolublepolycyclopentadiene by thorouzhiy agitating the reacpresentin the reaction mass. V

10. A process for producing benzene-soluble polycyclopentadiene by the catalytic polymerization of cyclopentadiene in the substantial absence of all other compounds polymerizable under. the conditions obtaining; comprising mixing with said cyclopentadlene inthe presence of an aromatic hydrocarbon solvent "of less than 8 carbon atoms to efiect said polymerization in considerable proportion .to *polycyclopentadiene a hydrolyzable -zinc.'chloride-organic solvent complex previously formed byreacting zinc chloride with an organic solvent capable of reacting with zinc chloride to i'orm' said hydrolyzable complex; and preventing the'polymerization of said cyclopentadiene from being'effected largely to benzene-insoluble polycyclopentadiene by thoroughly agitating the reaction mass while perature below C., the concentration of said cyclopentadiene below by weight, andthe proportion'oicatalyst to said cyclopentadiene below 10% by weight, and by stopping the reaction by inactivating said catalyst while-benzenesoluble polycyclopentadiene is the preponderant I polymer present in the reaction mass.

FRANK "J. SODAY.

maintaining the reaction tem- 

